Azomethine dyestuffs containing a heavy metal



Patented Apr. 22, 1941 ..UNITED STATES PATENT OFFICE AZOMETHINE DYE'STUFFS CONTAINING A HEAVYMET'AL Hans Krzikalla and Helmut Pfitzner, Ludwi shal'en on the Rhine, and Karl Schmidt, Germany, assignors to General Aniline & Film Corporation, a corpo- Cologne Muhlheim,

ration of Delaware No Drawing. Application April 7, 1938, Serial No. 200,674. In Germany April 16, 1937 6 Claims. Ql. 260-438) The present invention relates to azomethine dyestuffs containing a heavy metal.

We have found that new dyestuffs are obtained by causing primary aromatic amines containing at least one ortho-position to an amino group a radical capable of formin complexes with heavy metals having an atomic weight from 52 to 66 to react on ketones or aldehydes which also contain a radical of the said kind in orthoposition, the resulting substances being treated with agents supplying the said metals, if desired in the same working operation.

Radicals forming complexes with metals of the said kind are, for example, -OI-I--, Oalkyl,

hydroxy-2-naphthaldehyde, ortho-methoxybenzaldeh'yde, orthoaminobenzaldehyde, l-aminoanthraquinone 2 aldehyde, ortho-hydroxyacetophenone, ortho-aminoacetophenone, carbazoleortho-hydroxyaldehyde, anthracene-ortho-hydroxyaldehyde and their derivatives which may already be dyestufis. v

The starting materials should be so chosen that at least one contains at least one acid group, particularly a sulphonic group. In cases in which neither of the starting materials contains an acid group at most one of them shall contain as metal-sensitive group a hydroxyl group.

The substances containing sulphonic acid groups may be converted into the metal compounds by' treatment with agents supplying metals, as for example with chromium, copper or iron salts, working being carried on either at atmospheric or also increased pressure. The water-insoluble substances are converted into their metal compounds in organic solvents, as for example in the presence of anjalcohol or base of the nature of pyridine.

The dyestufis thus obtainable may be used for dyeing Wool, silk, leather, cotton, artificial silk or for the preparation of lacquers or artificial 1 fastness.

compositions. In chemical structure they are azomethines containin metal. Contrasted with the azomethines, which are generally speaking very sensitive to acid, they are so stable to acid that they are also suitable for dyeing in acid baths.

The following examples Will further illustrate how our said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 A chromium formate solution prepared from 37.2 parts of a 24.5 per cent chromium oxide paste, 19 parts of 85 per cent formic acid and 100 parts of water is added to a boiling mixture of 23.4 parts of 4-nitro-2-aminophenol-fi-sulphomc acid, 28 parts of crystallized sodium acetate and 12.2 parts of salicyl aldehyde and 200 parts of water. After boiling under reflux for about three hours, the solution is evaporated. The resulting compound may be salted out, filtered off by suction and dried.

The dyestuff corresponds to the probable formula The dyestuif is also formed when the reaction mixture is heated at 120 for 2 hours. It dyes wool, silk or leather level yellow shades of good If the preparation of the chromium compound is carriedout without the addition of sodium acetate the dyestuff is obtained in crystallized form. It dissolves very readily in nitrocellulose lacquers.

Instead of 4-nitro-2-aminophenol-6-sulphonic acid there may also be used 6-nitro-2-aminophenol-4-sulpl'1onic acid, 4-chlor-2-aminophenol-6- sulphonic acid, 2-aminophenol-4-sul-phonic acid, 4-methyl-2-aminophenol-6-sulphonic acid, 4- acetamino-2-aminophenol-6-sulphonic acid or 2- aminophenol-4,6-disulphonic acid, compounds giving yellow dyeings also being obtained. With 2,3-aminonaphthol-6-sulphonic acid a yelloworange dyestuff is obtained and with 1,2-aminonaphthol-4-sul-phonic acid a yellow-brownish dyestuii is obtained. Other chromium salts may be used instead of chromium formate.

, Example 2 A chromium iormate solution prepared from 2-hydroxynaphthaldehyde, ortho-aminobenzaldehyde or ortho-hydroxyacetophenone may be used instead of salicyl aldehyde, similar dyestuffs being obtained.

' Example 3 A mixture of 22.5 parts of 2-aminoanisol-4- sulphonic acid sodium salt, 12.2 parts of salicyl aldehyde, 37.2 parts of a 24.5 per cent chromium oxide paste, 19 parts of 85 per cent formic acid and 300 parts of Water is heated for 3 hours at 130 C. whereby the methyl group is split off and a chromium compound is formed. The mixture is then evaporated to dryness. The dyestuff thus obtained corresponds to that obtained from 2- aminophenol-l-sulphonic acid, salicyl aldehyde and chromium formate (see Example 1, last paragraph).

The dyestufi corresponds to the probable formula 5-nitro-2-anisidine-4-sulphonic acid or 1- amino-2-methoxynaphthalene-6-sulphonic acid may be used instead of 2-aminoanisol-4-sulphonic acid, and para-cresotinic acid aldehyde or ortho-methoxybenzaldehyde may be used instead of salicyl aldehyde. In all cases compounds similar to the said dyestuff are obtained.

Example 4 24.4 parts of salicyl aldehyde are added to a boiling solution of 20.4 parts of 2,6-diaminophenol--sulphonic acid and 28 parts of crystallized sodium acetate in 200 parts of water. After boiling for a short time or even simultaneously there is added a chromium formate solution corresponding to 9 parts of chromium oxide. After boiling for about four hours, the dyestuff is salted out with common salt, filtered off by suction and dried. It dyes wool, silk and leather fast orange shades. If an iron salt be used instead of chromium formate, a brown dyestuff is obtained.

The dyestuff corresponds to the probable formula 20.2 parts of 2-hydroXybenza1dehyde-5-sulphonic acid, 28 parts of crystallized sodium acetate and 19.9 parts of Z-aminophenol in 200 parts used 4-chlor-2-aminophenol,

of water are heated to boiling and a chromium formate solution is added which has been prepared from 37.2 parts of a 24.5 percent chromium oxide paste, 18 parts of per cent formic acid and parts of water. After boiling for several hours, the solution is evaporated. The dyestuff thus obtained dyes wool fast yellow shades.

The dyestuff corresponds to the probable formula H0.-.S CH=N--- Instead of 2-aminopheno1 there may also be 4-nitro-2-aminophenol, 4,6-dinitro-2-aminophen01, 6-nitro-4- chlor 2 aminophenol, 2,6 diamino-l-methylphenol and similar 2-aminophenols. From yellow to orange-brown shades of color are thus obtained A brown dyestufi is obtained with 2-hydroxy- 3-aminoanthraquinone.

Example 6 20.2 parts of 2-hydroxybenzaldehyde-5-sulphonic acid, 28 parts of crystallized sodium acetate and 10.8 parts of 3,3'-dihydroxy-4,4-di- 'aminodiphenyl are heated with 300 parts of water. There is then added a chromium formate solution corresponding to 9 parts of chromium oxide. After boiling for from 6 to 10 hours, the whole is filtered and the filtrate evaporated. The dyestuff obtained dyes wool brownish orange shades and also dyes viscose artificial silk.

The dyestufl corresponds to the probable formula By starting from 3,3 -dimethoxy-4A-diaminodiphenyl and heating the reaction mixture more strongly, the methyl groups are split off and the same dyestufi is obtained. With 4,4-diamino- 3,3'-dicarboxydiphen'yl a yellower shade of color is obtained.

Example 7 23.4 parts of 4-nitro-Z-aminophenol-G-sulphonic acid, 28 parts of crystallized sodium acetate and 17.2 parts of 2-hydroxy-1-naphthaldehyde are boiled with 300 parts of water and a chromium formate solution corresponding to 9 parts of chromium oxide added thereto. After boiling for several hours, the dyestuff containing chromium crystallizes out. After cooling the solution, it is filtered off by suction and dried. It dyes wool brownish orange shades.

The dyestuff corresponds to the probable formula The hydroxynaphthaldehyde yields a red dyestufi with 1.2-aminonaphthol-4-sulphonlc acid.

Similar dyestuffs are obtained with various 2- hydroxy-l-naphthaldehyde-monoand -di-sulphonic acids, as well as with l-hydroxy-Z-naphthaldehyde and its sulphonic acids.

Example 8 37.4 parts of the dyestuff obtainable by diazotizing 21.8 parts of 4-nitraniline-2-sulphonic acid and coupling with 12.2 parts of salicyl aldehyde are dissolved in 500 parts of water and there are then added at the boiling point 23.4 parts of 4-nltro-2-aminophenol-6-sulphonic acid, 28 parts of crystallized sodium acetate and a chromium formate solution coresponding to 9 parts of chromium-oxide. After boiling for 4 hours, the liquid is evaporated. The dyestufi dyes wool, silk and leather fast brown-orange shades.

The dyestufi corresponds tothe probable formula i The salicyl aldehyde or also, for example, 1- hydroxy-2-naphthaldehyde, may be coupled with a great variety of diazo compounds. In this way there may therefore be obtained a very large number of colored hydroxyaldehydes which in turn may be reacted with a great variety of ortho-aminophenols and metals.

The dyestuffs thus obtainable have varying afflnity for fibres which in some cases is very good, as for example afilnityffor' cotton, wool or artificial silk. By reason of the great variety of initial materials which may be used, the shades of color belong to all regions.

Example 9 Instead of 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid also -diaminodiphenylurea-3,3,'- dicarboxylic acid or 4,4'-diaminodiphenylmethane 3,3'-dicarboxylic acid,.and instead of 2-hydroxybenzaldehyde-5-sulphonic acid l-hydroxy- 2-naphthaldehyde-5-sulphonic acid or other hydroxynaphthaldehyde-sulphonic acids may be empolyed.

I Example 10 to the probable formula V-CH:

HOaS I Other 1,2-diamines suitable for the preparation of such dyestuffs are 1,2-diaminobenzenel-sulphonic acid, 4-nitro-1,2-diaminobenzene, 1,2-diaminonaphthalene, 1,2-diaminonaphthalene-5-sulphonic acid or 1,2-diaminoanthraquinone.

' Example 11 12.5 parts of Z-aminothiopheriol and 22.5 parts of the sodium salt of 2-hydroxybenzaldehyde-5- sulphonic acid are boiled in 200 parts of water. Then the mixture is heated to boiling with a solution of 37.2 parts of a 24.5 per cent chromium oxide paste in 100 parts ofwater and 19 parts of per cent formic acid for some hours. The dyestufi obtained by evaporating dyes leather and Wool yellow-brown shades.

The dyestuff corresponds to the probable formula 1 -O-(:JrS

l HOaS- cH=1 I A dyestuif which yields browner dyeings is obtained from 1-hydroxy-Z-naphthaldehyde-S-sulphonic acid.

Example 12 A mixture of :25 parts of the dyestuff from diazotized aniline and anthranilic acid (which may also be obtained from the formaldehyde bisulphite compound of anthranilic acid), 20.2 parts of 2hydroxybenzaldehyde-fiesulphonic acid, 28 parts of crystallized sodium acetate and a solution of chromium formate which corresponds to 9 parts of chromium oxide, is heated to boiling for some hours. Then the dyestufi is salted out and dried. It dyes wool and leather orangebrown shades.

The dyestuff corresponds to the probable formula 1 Similar dyestuffs are any other amines.

1 Example 13 A mixture of 8.1 parts of ortho-hydroxybenzaldehyde, 8.2 parts of ortho-anisidine, 12.2 parts of zinc acetate and 200 parts of 50 per cent aqueous ethanol is heated at 130 C. for 8 hours. The yellow dyestuff thus obtained is isolated, washed and dried. It may serve forexample for coloring lacquers. j

The dyestufi corresponds to the probable formula f Example 14 A mixture of 9.4 parts of the zinc salt of orthoamino-thiophenol, 10.2 parts of 2-hydroxy-1- naphthaldehyde, 240 parts of methanol is heated at 65 C. for 15 hours. The precipitate having a powerful yellow coloration is then filtered off by suction, washed with methanol and dried at about 70 C. The yield amounts to 15.6 parts.

The dyestufi corresponds to the probable formula Example 15 If instead of zinc acetate the corresponding amount of chromium acetate is used, 19'parts of a brown dyestuff are obtained.

Example 16 13.4 parts of the benzylidene compound of 2- hydroxy-l-naphthaldehyde and l-aminocarbazole are heated with 14.6 parts of zinc-acetate in 200 parts of methanol at 65 C. for about hours. The separated yellow zinc compound is filtered off by suction, washed with methanol and dried at about 80 C. Thus a yellow pigment is obtained which yields clear yellow shades if used for producing graphical prints. 4 Y

10.8 parts of zinc acetate and The dyestufi corresponds to the probable formula I r hat Example 17 A mixture of 14-parts of 2,4-dihydroxybenzaldehyde, 23.4 parts of the sodium salt of -nitroaminophenol-G-sulphonic acid, 250 parts of water and a solution of chromium formate (which is prepared accordingto the manner described in Example 1) is heated at 110 C. for an hour. After salting out a dyestufi is obtained which dyes wool uniform claret shades having good fastness properties as regards washing and fulling.

The dyestuff; corresponds to the probable formula son: OH O CrO I oH=1 I- Example 18 23.4 parts of 4-nitroaminophenol-6-sulphonic acid are diazotized and coupled with 14.5 parts of 2,4-dihydroxybenzaldehyde in a solution rendered alkaline by meansof sodium bicarbonate. Then the resulting dihydroxyazo dyestuff is salted out, filtered off by suction and reacted with an equimolecular proportion of 4- nitro-2-aminophenolfi-sulphonic acid by heating in aqueous solution. A solution of chromium formate prepared from 76 parts of a 24.5 per cent chromium oxide paste, 38 parts of -per cent formic acid and200 parts of water is added and the mixture is boiled under reflux for several hours. A dyestufi is obtained which dyes-leather and wool fast red-brown shades. V

. The dyestuff corresponds to the probable formula What we claim is:

1. A complex heavy metal compound'of an azomethine compound of the following general formula X and X standing in ortho-positions to the azomethine bridge, and n for a whole number up to 3, the heavy metal being selected from the heavy metals having an atomic weight of from 52 to 66.

2. A complex chromium compound of an emomethine compound of the following general formula wherein A and A stand for arylene radicals, the

hydroxyl groups standing in ortho-positions to the azomethine bridge, and n for a whole numher up to 3.

4. The complex chromium compound of the azomethine compound of the formula 5. The complex chrominum compound of the azomethine compound of the formula 6. The complex chromium compound of the azomethine compound of the formula c=N 01 v HANS KRZIKALLA. HELMUT PFITZNER. KARL SCHMIDT. 

